CN114392739A - Catalyst for degrading VOC (volatile organic compounds) in matt catalysis manner, preparation process and preparation device - Google Patents

Catalyst for degrading VOC (volatile organic compounds) in matt catalysis manner, preparation process and preparation device Download PDF

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CN114392739A
CN114392739A CN202210298404.8A CN202210298404A CN114392739A CN 114392739 A CN114392739 A CN 114392739A CN 202210298404 A CN202210298404 A CN 202210298404A CN 114392739 A CN114392739 A CN 114392739A
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catalyst
cavity
voc
heating system
nps
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杨胜洋
王涛
隋群
姜美仙
于军军
王琳
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Yantai Wotaite New Material Technology Co ltd
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Yantai Wotaite New Material Technology Co ltd
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Abstract

The invention relates to the technical field of cleaning, in particular to a photocatalyst for degrading VOC (volatile organic compounds) without photocatalysis, a preparation process and a preparation device. The catalyst is C-M1Ox‑M2Oy‑M3NPs, wherein x and y represent M in the catalyst respectively1Ox、M2OyThe x and y values are different with the catalyst base material and are 50 percent<x+y<60 percent; wherein M is1OxIs a first cocatalyst, M2OyAs a second cocatalyst, C represents the catalyst TiO2，M3NPs are metal nanoparticles. M3NPs are Ag nanoparticles. The catalyst for catalyzing and degrading VOC, the preparation process and the preparation device provided by the invention can degrade VOC under the dark condition, and can play an excellent degradation effect indoors or in the dark environment.

Description

Catalyst for degrading VOC (volatile organic compounds) in matt catalysis manner, preparation process and preparation device
Technical Field
The invention belongs to the technical field of cleaning, and particularly relates to a photocatalyst for degrading VOC (volatile organic compounds) without photocatalysis, a preparation process and a preparation device.
Background
With the increasing requirements of people on living environment, indoor environmental pollution has become a pain point in the public. More than 80% of modern urban people spend indoors, and the urban people seriously harm the health of people due to Volatile Organic Compounds (VOC) pollution represented by formaldehyde and benzene series and microbial pollution represented by bacteria. At present, the photocatalyst in the market can effectively degrade formaldehyde and the like only under the action of short-wavelength strong light, and is difficult to exert the degradation effect indoors or in a dark environment.
The Japanese photocatalytic father rattan island points out: weak visible light cannot effectively degrade VOCs if a photocatalyst is intended to be used indoors. In order to overcome the problem, the invention provides a catalyst with excellent performance, thereby realizing the technical effect of non-light degradation of VOC.
Disclosure of Invention
The invention aims to provide a photocatalyst for degrading VOC (volatile organic compounds) without photocatalysis, a preparation process and a preparation device, which solve the technical problem of how to degrade VOC in a dark condition and can exert the degradation effect in an indoor or dark environment.
A catalyst for degrading VOC by non-photocatalysis is C-M1Ox-M2Oy-M3NPs, wherein x and y represent M in the catalyst respectively1Ox、M2OyThe x and y values are different with the catalyst base material and are 50 percent<x+y<60%；
Wherein M is1OxIs a first cocatalyst, M2OyAs a second cocatalyst, C represents the catalyst TiO2，M3NPs are metal nanoparticles.
M1OxThe content of (A) is 45%<x<55 percent, and the specific element is any one of Al, Ca and Fe;
M2Oythe content of (A) is 5%<y<15 percent, and the specific element is any one of Co, Ni and Ce;
M3NPs are Ag nanoparticles and are present in an amount of 5%.
A preparation process of a catalyst for degrading VOC without photocatalysis comprises the following specific steps:
step S1: by molecular assembly, catalysisConstructing organic-inorganic ordered composite photocatalytic material by chain transfer polymerization and multistage heat treatment technology to obtain catalyst C-M1Ox-M2Oy-M3NPs；
Step S2: and performing catalysis test characterization on the prepared photocatalyst, and constructing an internal relation between catalysis strength and dosage.
In the step S1, titanium tetrachloride and the basic metal oxide M are added during molecular assembly1Ox-M2Oy reaction, namely, completing the selective self-assembly process of three types of nanoparticles under the slightly alkaline pH condition by utilizing the violent reaction of acid-base property;
during catalytic chain transfer polymerization, adding acrylic acid modified silver nitrate into a system completed by molecular assembly, adding an AIBN photoinitiator, carrying out light reaction for 10 hours in an anaerobic state, and after the reaction is finished, separating and drying to obtain a solid;
during the multi-stage heat treatment, the obtained solid components are respectively dried, thermally decomposed, thermally roasted and finally introduced with a hydrogen source for activation and regeneration treatment.
The multistage heat treatment comprises the following specific steps:
(1) maintaining the refined particles at a low temperature of 300-350 ℃ for 2-5 hours in a nitrogen gas atmosphere;
(2) on the basis of the step (1), maintaining the temperature of 450-550 ℃ for 3-5 hours;
(3) maintaining the temperature of 1000-1200 ℃ for 1-2 hours on the basis of the step (2), and then slowly cooling;
(4) grinding and spheroidizing the obtained particles on the basis of the step (3);
(5) and (4) on the basis of the step (4), introducing hydrogen into the tubular furnace at the temperature of 450-550 ℃ for carrying out catalyst activation treatment.
In the step S2, when the catalyst is tested and characterized, the valence state of the XPS element and the TPR oxygen vacancy of hydrogen are observed, the adsorption amount of the catalyst is tested by a physical adsorption instrument, the specific surface area of the catalyst is measured by a BET test method, and the porosity is tested by nitrogen adsorption and desorption.
Wherein XPS represents X-ray photoelectron spectroscopy.
A device for preparing a photocatalyst without photocatalytic degradation of VOC comprises a preparation platform, an oxygen-free chamber structure and a heating system, wherein the oxygen-free chamber structure and the heating system are arranged on the preparation platform;
the oxygen-free chamber structure and the heating system are both connected with a nitrogen cylinder, the heating system is connected with a hydrogen source, the solid-liquid separator is arranged above the first cavity, and the first cavity is communicated with the heating system.
The anaerobic chamber structure comprises a cavity II arranged on the preparation platform, a rotating plate with one end hinged to the upper edge of the cavity II, and a capsule arranged outside the rotating plate, wherein a through hole is formed in the rotating plate and communicated with the capsule, an air outlet pipe is arranged on the capsule, and an electromagnetic valve is arranged on the air outlet pipe; and a light source is arranged on the inner side surface of the rotating plate.
The heating system comprises a heating furnace and a furnace cover arranged on the heating furnace, the heating furnace and the furnace cover are arranged in a cavity III, and an upper cover is arranged at an opening at the upper end of the cavity III;
the cavity III is communicated with the nitrogen cylinder and the hydrogen source, the cavity III is communicated with the cavity I, and a sealing cover is arranged at an opening at the outer end of the cavity I.
Compared with the prior art, the invention has the beneficial effects that:
(1) the organic-inorganic ordered composite catalytic material (C-M) is constructed by utilizing the techniques of molecular assembly, solvothermal, multistage heat treatment and the like1Ox-M2Oy-M3NPs) is added into the coating, so that the antibacterial function of the coating can be realized while the VOC (volatile organic compounds) is efficiently degraded, common cocci, bacilli and spirochetes can be effectively killed, and the C-M prepared by the method1Ox-M2Oy-M3The NPs composite catalyst has the characteristics of narrow energy band, good photoelectron transmission performance, wide photoresponse range and the like, and has the effect only under strong light and short wavelength light compared with the photocatalyst on the marketThe optical response wavelength of the product can be expanded to more than 800 nm, and the purposes of VOC degradation and antibiosis can be still realized under the conditions of no light and weak light.
(2) The novel ternary composite catalyst can degrade VOC (volatile organic compounds) through room temperature, water vapor and illumination and achieve the aim of sterilization, obviously improves the air quality in a closed space and reduces microbial pollution, and has very wide development prospect and long ecological cycle.
(3) The catalyst preparation device provided by the invention integrates chemical reaction, heating and solid-liquid separation on one preparation platform, wherein a heating system can complete a plurality of heating procedures, has a multifunctional technical effect, and greatly saves the floor area of equipment.
Drawings
FIG. 1 is a first structural view of a catalyst preparation apparatus according to an embodiment of the present invention.
FIG. 2 is a second structural view of a catalyst preparation apparatus in an example of the present invention.
Wherein: 1. preparing a platform; 2. a closure cap; 21. a first cavity; 3. a rotating plate; 31. a second cavity; 4. a capsule; 5. an air outlet pipe; 6. a solid-liquid separator; 7. a nitrogen gas cylinder; 71. a first pipeline; 72. a second pipeline; 8. an upper cover; 81. a third cavity; 82. a furnace cover; 83. heating furnace; 9. a source of hydrogen gas; 91. a third pipeline; 10. an oxygen-free chamber structure; 11. a heating system.
Detailed Description
In order to make the technical features of the present invention more apparent, the present invention is described below in detail by way of embodiments.
A catalyst for degrading VOC by non-photocatalysis is C-M1Ox-M2Oy-M3NPs, wherein x and y represent M in the catalyst respectively1Ox、M2OyThe x and y values are different with the catalyst base material and are 50 percent<x+y<60%；
Wherein M is1OxIs a first cocatalyst, M2OyAs a second cocatalyst, C represents the catalyst TiO2，M3NPs are metal nanoparticles.
M1OxThe content of (A) is 45%<x<55 percent, and the specific element is any one of Al, Ca and Fe;
M2Oythe content of (A) is 5%<y<15 percent, and the specific element is any one of Co, Ni and Ce;
M3NPs are Ag nanoparticles and are present in an amount of 5%.
M1And M2The metal oxide is used as a promoter for improving the overall toughness of the catalyst, improving the overall activity of the catalyst and slowing down the occurrence and spread of poisoning effects, so that some metal oxides with high physical strength and strong chemical properties are selected.
M1OxMeanwhile, the formaldehyde-free environment-friendly food additive is a food additive, can efficiently degrade formaldehyde under the conditions of room temperature, no light and certain humidity, is a mild oxidant and is very environment-friendly.
M2OyCan degrade formaldehyde under weak sunlight intensity.
M3NPs have excellent antibacterial properties and surface plasmon resonance effects.
C-M1Ox-M2Oy-M3The action mechanism of NPs for removing formaldehyde is as follows: m3The NPs have surface plasmon resonance effect to give M2OyWider light absorption range and weak light utilization performance, so that M2OyCan degrade formaldehyde under the light intensity of 0.01 sunlight. Even at night in the absence of light, M1OxCan also degrade formaldehyde under the conditions of room temperature and certain humidity.
A preparation process of a catalyst for degrading VOC without photocatalysis comprises the following specific steps:
step S1: the organic-inorganic ordered composite photocatalytic material is constructed by utilizing the techniques of molecular assembly, catalytic chain transfer polymerization and multistage heat treatment to obtain the catalyst C-M1Ox-M2Oy-M3NPs；
Step S2: and performing catalysis test characterization on the prepared photocatalyst, and constructing an internal relation between catalysis strength and dosage.
The coating is an interior wall coating, and the catalyst is uniformly mixed in the coating and then used for coating and painting.
In step S1, titanium tetrachloride and a basic metal oxide M are added during molecular assembly1Ox-M2Oy reaction, namely, completing the selective self-assembly process of three types of nanoparticles under the slightly alkaline pH condition by utilizing the violent reaction of acid-base property;
during catalytic chain transfer polymerization, adding acrylic acid modified silver nitrate into a system completed by molecular assembly, adding an AIBN photoinitiator, carrying out light reaction for 10 hours in an anaerobic state, and after the reaction is finished, separating and drying to obtain a solid;
during the multi-stage heat treatment, the obtained solid components are respectively dried, thermally decomposed, thermally roasted and finally introduced with a hydrogen source 9 for activation and regeneration treatment.
The self-assembly process can be realized without other operations, and is not detailed herein;
in the operation of separating and drying to obtain a solid, the system assembled by adding the silver nitrate modified by acrylic acid to the molecule is still liquid, and at this time, a centrifuge or a filter is required to separate solid from liquid, and since the catalyst is in the solid, the wet solid obtained also requires the steps of drying, grinding and refining.
The multistage heat treatment comprises the following specific steps:
(1) maintaining the refined particles at a low temperature of 300-350 ℃ for 2-5 hours in a nitrogen gas atmosphere;
(2) on the basis of the step (1), maintaining the temperature of 450-550 ℃ for 3-5 hours;
(3) maintaining the temperature of 1000-1200 ℃ for 1-2 hours on the basis of the step (2), and then slowly cooling;
(4) grinding and spheroidizing the obtained particles on the basis of the step (3);
(5) and (4) on the basis of the step (4), introducing hydrogen into the tubular furnace at the temperature of 450-550 ℃ for carrying out catalyst activation treatment.
In step S2, when the catalyst is tested and characterized, the valence state of the XPS element and the TPR oxygen vacancy of hydrogen are observed, the adsorption amount of the catalyst is tested by a physical adsorption instrument, the specific surface area of the catalyst is measured by a BET test method, and the porosity is tested by nitrogen adsorption and desorption. Wherein, table 1, table 2 and table 3 are tables of VOC concentrations of catalytic degradation under the conditions of no light and weak light of the catalyst provided in the present scheme, respectively, from which it can be seen that, through the no-light catalytic degradation, the concentration values of VOC are all greatly reduced, the final residual quantity of some pollutants even reaches the negligible degree, and the adsorption quantity of the physical adsorption apparatus is the concentration after the treatment subtracted from the allowable emission concentration; in addition, it can be seen that the effect of non-photocatalytic degradation is close to or substantially similar to that of low-light, light-conditioned degradation.
TABLE 1 concentration table of catalytic degradation VOC of catalyst in absence of light
Figure DEST_PATH_IMAGE001
TABLE 2 VOC concentration in the catalyst under low light conditions
Figure 203823DEST_PATH_IMAGE002
TABLE 3 table of VOC concentrations catalytically degraded by the presence of light in the catalyst
Figure DEST_PATH_IMAGE003
Referring to fig. 1 and 2, a device for preparing a catalyst without photocatalytic degradation of VOCs comprises a preparation platform 1, an oxygen-free chamber structure 10 and a heating system 11, wherein the oxygen-free chamber structure 10 and the heating system 11 are arranged on the preparation platform 1, and a solid-liquid separator 6 is arranged between the oxygen-free chamber structure 10 and the heating system 11;
the oxygen-free chamber structure 10 and the heating system 11 are both connected with a nitrogen cylinder 7, the heating system 11 is connected with a hydrogen source 9, the solid-liquid separator 6 is arranged above the first cavity 21, and the first cavity 21 is communicated with the heating system 11.
The anaerobic chamber structure 10 comprises a cavity II 31 arranged on the preparation platform 1, a rotating plate 3 with one end hinged on the upper edge of the cavity II 31, and a capsule 4 arranged on the outer side of the rotating plate 3, wherein a through hole is arranged on the rotating plate 3, the through hole is communicated with the capsule 4, an air outlet pipe 5 is arranged on the capsule 4, an electromagnetic valve is arranged on the air outlet pipe 5, and a light source is arranged on the inner side surface of the rotating plate 3.
The heating system 11 comprises a heating furnace 83 and a furnace cover 82 arranged on the heating furnace 83, the heating furnace 83 and the furnace cover 82 are arranged in a cavity III 81, and an upper cover 8 is arranged at an opening at the upper end of the cavity III 81;
the cavity III 81 is communicated with the nitrogen cylinder 7 and the hydrogen source 9, the cavity III 81 is communicated with the cavity I21, and the outer end opening of the cavity I21 is provided with a sealing cover 2.
The nitrogen cylinder 7 is connected with the second cavity 31 through a first pipeline 71 and is connected with the third cavity 81 through a second pipeline 72, the hydrogen source 9 is connected with the third cavity 81 through a third pipeline 91, and an electromagnetic valve can be arranged on the pipeline to control the on-off.
The specific working process of the invention is as follows:
during molecular assembly, titanium tetrachloride and basic metal oxide M are mixed1Ox-M2The Oy reaction realizes the selective self-assembly process of the three types of nanoparticles under the pH condition of alkalescence by utilizing the violent acid-base reaction, at the moment, the reaction process can be placed in the second cavity 31, and the air outlet pipe 5 on the capsule 4 is opened under the sealing action of the rotating plate 3, so that the protection effect can be achieved, and the harm to the body of people caused by the violent acid-base reaction can be avoided;
during catalytic chain transfer polymerization, adding acrylic acid modified silver nitrate into a system completed by molecular assembly, adding an AIBN photoinitiator, carrying out light reaction for 10 hours in an anaerobic state, and after the reaction is finished, separating and drying to obtain a solid; in order to generate an oxygen-free environment, opening a nitrogen bottle 7, covering a rotating plate 3, opening an air outlet pipe 5 on a capsule 4, continuously introducing nitrogen into a second cavity 31, discharging oxygen, closing an electromagnetic valve on the air outlet pipe 5, continuously introducing nitrogen until the capsule 4 swells and reaches a certain volume, closing the nitrogen bottle 7, knowing that the second cavity 31 is basically in the oxygen-free environment, opening a light source on the rotating plate 3 to perform illumination reaction, wherein the nitrogen in the second cavity 31 can possibly escape because the length of the nitrogen reaches 10 hours, judging according to the volume of the capsule 4, opening the nitrogen bottle 7 again when the volume of the capsule 4 is reduced, introducing nitrogen, and repeating the steps;
after the illumination reaction is finished, a dry solid needs to be separated, and at the moment, a centrifuge or a filter is needed to realize solid-liquid separation, namely the solid-liquid separator 6 in the invention, the illumination reaction product is placed in the solid-liquid separator 6, and after the separation is finished, the obtained wet solid also needs to be subjected to the processes of drying, grinding and refining, wherein in the drying process, the cavity I21 is communicated with the cavity III 81, and the heat in the heating furnace 83 enters the cavity I21 and contacts with the solid-liquid separator 6, so that the drying process is realized, convenience and rapidness are realized, and energy is saved;
during the multi-stage heat treatment, the obtained solid components are respectively dried, thermally decomposed, thermally roasted and finally introduced with a hydrogen source 9 for activation and regeneration treatment.
The technical features of the present invention which are not described in the above embodiments may be implemented by or using the prior art, and are not described herein again, of course, the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and variations, modifications, additions or substitutions which may be made by those skilled in the art within the spirit and scope of the present invention should also fall within the protection scope of the present invention.

Claims (9)

1. The catalyst for degrading VOC (volatile organic compounds) without photocatalysis is characterized by comprising
C-M1Ox-M2Oy-M3NPs, wherein x and y represent M in the catalyst respectively1Ox、M2OyThe x and y values are different with the catalyst base material and are 50 percent<x+y<60%；
Wherein M is1OxIs a first cocatalyst, M2OyAs a second cocatalyst, C represents the catalyst TiO2，M3NPs are metal nanoparticles.
2. The non-photocatalytic VOC degradation catalyst of claim 1, wherein M is M1OxThe content of (A) is 45%<x<55 percent, and the specific element is any one of Al, Ca and Fe;
M2Oythe content of (A) is 5%<y<15 percent, and the specific element is any one of Co, Ni and Ce;
M3NPs are Ag nanoparticles and are present in an amount of 5%.
3. A preparation process of a catalyst for degrading VOC without photocatalysis is characterized by comprising the following specific steps:
step S1: the organic-inorganic ordered composite photocatalytic material is constructed by utilizing the techniques of molecular assembly, catalytic chain transfer polymerization and multistage heat treatment to obtain the catalyst C-M1Ox-M2Oy-M3NPs；
Step S2: and performing catalysis test characterization on the prepared photocatalyst, and constructing an internal relation between catalysis strength and dosage.
4. The process for preparing a catalyst for degrading VOC without photocatalysis according to claim 3, wherein in the step S1, titanium tetrachloride and the basic metal oxide M are added during molecular assembly1Ox-M2Oy reaction, namely, completing the selective self-assembly process of three types of nanoparticles under the slightly alkaline pH condition by utilizing the violent reaction of acid-base property;
during catalytic chain transfer polymerization, adding acrylic acid modified silver nitrate into a system completed by molecular assembly, adding an AIBN photoinitiator, carrying out light reaction for 10 hours in an anaerobic state, and after the reaction is finished, separating and drying to obtain a solid;
during the multi-stage heat treatment, the obtained solid components are respectively dried, thermally decomposed and thermally roasted, and finally, a hydrogen source (9) is introduced for activation and regeneration treatment.
5. The process for preparing a catalyst for the photocatalytic degradation of VOCs in the absence of light according to claim 4, wherein the specific steps of the multistage heat treatment are as follows:
(1) maintaining the refined particles at a low temperature of 300-350 ℃ for 2-5 hours in a nitrogen gas atmosphere;
(2) on the basis of the step (1), maintaining the temperature of 450-550 ℃ for 3-5 hours;
(3) maintaining the temperature of 1000-1200 ℃ for 1-2 hours on the basis of the step (2), and then slowly cooling;
(4) grinding and spheroidizing the obtained particles on the basis of the step (3);
(5) and (4) on the basis of the step (4), introducing hydrogen into the tubular furnace at the temperature of 450-550 ℃ for carrying out catalyst activation treatment.
6. The process of claim 5, wherein in step S2, during the characterization of the catalyst test, the valence state of XPS element and TPR oxygen vacancy of hydrogen are observed, the adsorption amount of the catalyst is tested by physical adsorption apparatus, the specific surface area of the catalyst is measured by BET method, and the porosity is tested by nitrogen adsorption and desorption.
7. The device for preparing the catalyst for degrading VOC without photocatalysis is characterized by comprising a preparation platform (1), an oxygen-free chamber structure (10) and a heating system (11), wherein the oxygen-free chamber structure (10) and the heating system (11) are arranged on the preparation platform (1), and a solid-liquid separator (6) is arranged between the oxygen-free chamber structure (10) and the heating system (11);
the anaerobic chamber structure (10) and the heating system (11) are both connected with a nitrogen cylinder (7), the heating system (11) is connected with a hydrogen source (9), the solid-liquid separator (6) is arranged above the first cavity (21), and the first cavity (21) is communicated with the heating system (11).
8. The device for preparing the catalyst for degrading VOC without photocatalysis according to claim 7, wherein the oxygen-free chamber structure (10) comprises a second cavity (31) arranged on the preparation platform (1), a rotating plate (3) with one end hinged to the upper edge of the second cavity (31), and a capsule (4) arranged on the outer side surface of the rotating plate (3), the rotating plate (3) is provided with a through hole which is communicated with the capsule (4), the capsule (4) is provided with an air outlet pipe (5), and the air outlet pipe (5) is provided with an electromagnetic valve;
and a light source is arranged on the inner side surface of the rotating plate (3).
9. The photocatalyst-free device for degrading VOC according to claim 8, wherein said heating system (11) comprises a heating furnace (83), a furnace cover (82) disposed on said heating furnace (83), said heating furnace (83) and said furnace cover (82) are disposed in a cavity III (81), and an upper cover (8) is disposed at an upper end opening of said cavity III (81);
the cavity III (81) is communicated with the nitrogen gas cylinder (7) and the hydrogen source (9), the cavity III (81) is communicated with the cavity I (21), and a sealing cover (2) is arranged at an opening at the outer end of the cavity I (21).
CN202210298404.8A 2022-03-25 2022-03-25 Catalyst for degrading VOC (volatile organic compounds) in matt catalysis manner, preparation process and preparation device Pending CN114392739A (en)

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